Process for breaking petroleum emulsions



ganic salts, from Feb. I,

PROCESS FOR BREAKING PETROLEUM 'EMULSIONS Melvin De G oote,

Kirkwood,Mo.,

No Drawing. Application April University City, (1 Keiser, Webster Groves, and Arthur F.

assignors to Petrolite Corpora on, -Del., a corporation of Wirtel,

I Serial No. 440,751 5 Claims. (Cl. 252-340) I This invention relates primarily to the resolution of petroleum emulsions.

One object of our invention is to provide a novel process for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as "cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

Another object is to provide an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude petroleum and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned, is of significant value in removing impurities, particularly inorpipeline oil.

The composition of matter that is used as the demulsifier of our process is obtained by the hydroxyacetylation of a drastically oxidized dehydrated ricinoleicacid compound of the kind hereinafter described, particularly a drasticallyoxidized dehydrated castor oil.

.The expression ricinoleic acid compounds" is intended to refer to ricinoleic acid, polyricinoleic acid, and particularly, the glycerides of ricinoleic acid. Specifically, the expression includes monoricinolein, dirlcinolein, ricinoleic acid, etc. Cas- 90% of triricinolein, and due to its availability and low cost, is the preferred raw material.

It is well knownthat ricinoleic compounds which have not been subjected to pyrolytic dehydration, may be oxidized in various manners. This is usually accomplished by subjecting a ricinoleic compound to treatment, such as, blowing with a suitable gaseous oxidizing medium, i. e., air, oxygen, ozone, or ozonized air. Such oxidation is commonly carried out at ordinary or superatmospheric pressure (up to about 200 pounds per square inch) either moist or dry; and in the presence of or absence of a catalyst,'such as lead oieate, cobalt linoleate, or m anese oieate, or such 'as alpha-pinene. or linseed oil, etc. Care should be taken, however, not to permit temperature rise such that excessive propylic decomposition would take place. The oxidation may be vigorous. as by vigorous blowing, or may be more gradual, as by exposure in thin films to air,

provided the oxidation is sufilciently prolonged to I obtain thedesired drastic oxidation. Usually, the time required is at least about 8 to 10 hours under conditions most favorable to oxidation, 1. e., blowing at a relatively high temperature, and for certain fatty compounds much more prolonged oxidation, i. e., several days, or even weeks, is desirable, especially under conditions less favorable to rapid oxidation. In any event, whether the oxidation is produced by continued mild oxidation, or by more vigorous oxidation, a condition of drastic oxidation is indicated by changes in chemical and physical attributes of the material. These changes are usually indicated by a lowered iodine value, an increased saponification value,

' specific gravitinand an number may become less 1 tor oil of commerce contains approximately 85- usually an increased acetyl value, an increased increased refractive index. Thus, the iodine than 70, and even as low as about 40. The saponification value may be about 215 to about 283, and the acetyl value may be about to about 200. The viscosity is increased and the drastically-oxidized product may become very heavy and stifi at ordinary temperatures. The refractive index is also increased. The color of the drastically-oxidized material may be a pale yellow or light amber, or may be a deep orange color. If oxidation is carried on long enough a product of liver-like consistency and dark color is obtained.

The same sort of procedure which is used to oxidize ricinoleic acid compounds which have not been subjected to pyrolytic dehydration, such as ordinary castor oil of commerce, may also be employed to oxidize dehydrated castor oil, or similar material of the kind herein intended as a primary raw material. Generally speaking,

however, the following kept in mind:

Such materials are apt to contain at least significant amount of octadecadiene 9,1l-acid-1 or its ester, which is recognized as a powerful catalyst for promoting oxidation of castor oil or similar materials. Thus, it is rarely necessary to modifications should be vadd any catalyst to hasten oxidation. Furthermore, it is rarely necessary to oxidize under pressure, although such procedure may be employed. It is rarely necessary to use oxygen instead of air. It is rarely necessary to oxidize at a temperature above 120 C. Thus, notwithstanding the fact that any of the usual procedures employed for oxidizing castor oil may be employed for oxidizing dehydrated castor oil, yet generally spc aking, considerably less drastic conditions are required. Furthermore, the time element can be decreased greatly. The same sort of apparatus and the same sort of procedure is employed as in the case of conventional oxidation of castor oil. Since dehydrated castor oil is already polymerized to a greater or lesser degree, and perhaps has initial viscosity considerably greater than that of castor oil, it is obvious that the final stages of oxidation must be carried out more cautiously, and that excessive oxidation may produce a solid or spongy or rubber-like material without previous indication of the imminent critical stage. In any event, the material prior to oxidation should be analyzedand oxidation should be conducted until there is a significantchange, as indicated by increase in viscosity, change in such indices as iodine number, hy-

cially and used in other arts which have no parfor instance, as substitutes for drying oils, as plasticizers in the manufacture of resins, as ingredients entering into the compounding of insulating materials, etc. Generally speaking, the conventional procedure is to subject a quantity of castor oil to destructive distillation, approxi- 40 mately 250 310 (3., and generally, 250-285 C., until at least 5-15% of the original volume has been removed as a distillate. Sometimes the procedure is conducted primarily to recover the distillate, due to its high content of heptaldehyde. 45

Generally speaking, the lower limits of the ma, terial distilled oil are approximately -10%, and the upper limits, possibly 15-23%. In some instances, pyrolysis is conducted in presence of an added catalyst, which may permit the reaction, 1. e., the degradation or destructive distillation, to take place at lower temperature; and sometimes vacuum is employed or both vacuum and a catalyst. Such procedure of subjecting a ricinoleic acid compound, and especially ricinoleic acid or castor oil, to a pyrolysis, is so well known that no further elaboration is required. However, for convenience, reference is made to the following patents, which clearly describe the prohydroxyi lowing identifying characteristics within the ranges indicated:

Acid number 14.0 to 25.0 Saponification number 195 to 240 5 Iodine number 70 to 95 Hydroxyl number 63.0 to 80.0

Reichert-Meisel number Less than 5 Acetyl number to 75 Percent unsaponifiable matter-" Generally less than 3 Percent nitrogen 0.0 Percent SO: 0.0 Percent ash Trace Specific gravity at 31 C About 0.9574 15 Refractive index at 31 c About 1.495

Color Straw or light amber A specific example of a' very desirable oxidized dehydrated castor oil for use in the practice of this invention and which is available in the open market, has approximately the following specific characteristics:

, Acid n er 18.1 droxylnumber, etc., all of which is obvious to .saponmcauon number 5' those skilled in the art. As a matter of tact, 25 Iodine number 83 unless one desires to do so, there is no need to Acetyl as oxidize such dehydrated castor oil, insofar that nydmxyl number 7L4 various products oi? this kind are sold commer- Reichert Me1se1 number 2 I Percgzt unsaponifiable matter than 2.5

ticular connection with the usage herein n- 3 prg t, mg n 0.0 templated. "Percent S02 M) Castor Oil or similar materials of the kind .de--' Percent ash Trace scribed have been dehydrated. an s h yspecific gravity t 31 0 0.9574 drated materials used for various o her purp Refractive index t. 31 0 1.4795

The above values or similar values are of assistance in indicating and characterizing a materlal of the kind herein contemplated. For instance, although the entire chemistry of the dehydration of castor oil is not known, yet obvious- 1y, there must be a marked reduction in the acetyl or hydroxyl value, and simultaneously an increase in the iodine value. Also, such pyrolytic reaction tends to eliminate the low molal or volatile acids. On oxidation of such material, the acetyl value or hydroxyl value may stay constant or increase. But, in any event, the iodine value is reduced until it begins. to approximate that of castor oil or ricinoleic acid prior to de- 5 hydration, or somewhat lower. The fact that the acety1= value or hydroxyl value does not increase proportionally with the drop in the iodine value is, of course, due to either the formation of ether type compounds, or'oxldes which do not give a or acetyl value, or else, due to the formation of ester acids or similar reactions. It is generally desirable that the iodine number of the drastically-oxidized dehydrated castor oil be hot les than 70, that the saponiflcation value be cedure, and in some instances, point out at least 0 Within the range 195 to 200 and h h a etyl some of the complicated chemical changes that take place:

U. S. Patents No. 1,240,565, Harris. September 18, 1917; No. 1,749,463, Bertsch, March 4, 1930;

value be within the range 0! 60 to 75.

The production of hydroxyacetylated drastically oxidized dehydrated castor oil, or a similar type of compound, is comparatively simple and is No. 1,799,420,.Holton, April 7, 1931; No. 1,886,539, comparable to the manufacture of acetylated Fanto, November 8, 1932; No. 1,892,258, Uier, December 27,1932; No. 2,156,737, Priester, May 2, 1.939; No. 2,195,225, Priester', March. 26, 1940; British No. 306,452, Scheiber, May 9, 1930.

As to a comparative evaluation of various dehydration catalysts Ior castor oil, see Masloboino- Zhirovanya Prom. 16, No. 5/6, 33-8 (1940).

The products which we prefer to use as reactants in the present instance, are blown dehydrated castor oils having substantially the 101- tant.

tor oil is characterized by the presence of'a hy-- caster oil, except that hydroxyacetic acid appears to be more reactivethan acetic acid, and instead of using castor oil, one employs drastically-oxidized dehydrated castor oil as a reac- Since drastically-oxidized dehydrated casdroxyl group or groups, as indicated by thehydroml value or number, it is obvious that eateriilcation must take place, and thus the reactant is conducted in such a'manner and under such conditions as to promote esterification and remove any water formed. The usual procedures an inert dried gas through the reacting mixture;

at other times esterification may be conducted in the presence of a high boiling water-insoluble solvent, such as xylene or the like, which assists in removing the water in the form of vapors; the

condensate so derived, both from the water vapor and solvent vapor, is separated by gravity; and the solvent returned to the reacting chamber for further use,

The selection of suitable amounts of reactants in the manufacture of hydroacetylated drasti- 2 cally-oxidized dehydrated castor oil or the like, is, of course, simple. One may select a drastically-oxidized dehydrated castoroil corresponding,

example, to the type previously described by .nalytical values. The hydroxyl or acetyl value or number includes the hydroxyl groups attached to each of the high molal acyl radicals present. The chemical cha' ges Occurring in the manufacture of drastically-oxidized dehydrated castor oil ndicate that the final product is, in essence, a

glsperide, or at least, to the extent of a majority percentage. that the hydroxyl groups may be distributed more or less uniformly in regard to the three high" molal acyl radicals present in such glyceride.

For convenience, in the present instance, one may consider such product as'comparable to triricinolein, and as if it were a trihydric alcohol. From triricinolein one can obtain mono-hydroxyacetylated triricinolein, di-hydroxyacetylated triricin- 40 olein, and trihydroxyacetylated triricinolein. ,Similarly, based on molar proportions, one can obtain a mono-hydroxyacetylated drasticallyoxidized dehydrated triricinolein, a di-hydroxyacetylated drastically-oxidized dehydrated triricinolein, and a tri-hydroxyacetylated drastically-oxidized dehydrated triricinolein. For prac-- tical purposes, of course, there is no economical justification for obtaining a technically pure triricinolein, subjecting such material to dehydration, and then to drastic oxidation, and'flnally to hydroxyacetylation. For practical purposes, we prefer to use castor oil as the initial raw material. Actually, one is not limited to the stoi- -chiometric proportions, for we have found that a moderate excess of. hydroxyacetic acid may be employed, over and above the amount indicated by the acetyl number or value.

Thus, the'product particularly contemplated in pounds obtained by the hydroxyacetylation of drastically-oxidized dehydrated castor oil. For purposes of convenience, reference will be made to mono-hydroxyacetylated drastically-oxidized dehydrated castor oil, di-hydroxyacetylated drastica1ly-oxidized dehydrated castor oil, and trihydroxyacetylated drastically-oxidized dehydrated castor oil. Examination of the reaction indicates that water is formed and must be removed. Actually, the water formed may not necessarily be removed instantly, and thus, may undergo certain other obvious reactions. Like-' 'wise, for reasons of economy, it may be desirable to use a highly concentrated hydroxyacetic acid instead of the anhydrous material as the selected 75.

With this in mind, it is. apparentreactant. In such instances, the water would er-glycerides of the drastically-oxidized dehydrated castor oil. Glycerolmay also 'be present,

but it is not intended in the present instance to claim the product obtained or reaction between hydroxyacetic acid and glycerol, but it is to be noted that such material may be present cogenerically, for reasons indicated.

The lower-glycerides are comparable to monoolein or di-olein, and are referred to generically I as superglycerinated fats, or more specifically,

superglycerinated triricinolein, or superglycerinated castor oil. In the present instance, the proper nomenclature would be superglycerinated drastically-oxidized dehydrated castor oil. Actually, if one desired, such products or compounds need not be obtained by hydrolysis, but one could treat one mole of drastically-oxidized dehydrated castor oil with one or two moles of glycerol in the customary manner, so as to cause rearrangement to take place, i. e., so as to obtain the lower glycerides.

Earlier reference to the compounds herein contemplated, and particularly for use as a demulsifier, included the hydroxyacetylated derivatives of drastically-oxidized dehydratedricinoleic acid compounds. In view of what has been said, such compounds are now suitably limited to drasticall'y-oxidizeddehydrated castor oil, drasticallyoxidized dehydrated triricinolein, drastically-oxidized dehydrated diricinolein, drastically-oxidized dehydrated mono-olein, and the estolides of drastically-oxidized dehydrated castor oil, together with drastically-oxidized dehydrated ricinoleic acid and polyricinoleic acid.

Although it is believed that in view of what has been said,that no further description is necessary in regard to the manufacture of hydroxyacetylated drastically-oxidized dehydrated castor oil, or similar compounds, the following examples are included'by way of illustration:

Hydroxyacetylated drastically-oxidized dehydrated castor oilE.1:ampZe 1 reaction is conducted at 200-250 degrees centithe present instance, is the compound or com- 60 to give substantially a mono-hydroxyacetylated blown dehydrated castor oil.

Hydroxyacetylated drastically-Oxidized deli 11 drated castor oil-Ea gmple 2 The same procedure is employed'as' in Ex:

The amount of hydroxyacetic acid.

ample 1, preceding, except that twice the amount of hydroxyacetic acid is employed so as to obtain a, dihydroxyacetylated blown dehydrated castor oil.

Hydroximcetylated drastically oxidized dehydrated castor oil-Example 3 The same procedure is followed as in Example 1, preceding, except that three times the amount of hydroxyacetylated castor oil is employed so as to yield substantially a tri-hydroxyacetylated blown dehydrated castor oil.

Hydroruacetylated drastically oxidized dehydrated castor oib-Exqmple 4 The same procedure is followed as in Examples 1 to 3, preceding, except that anhydrous hydroxyacetic acid is employed and water is removed immediately upon formation. The product so obtained represents hydroxyacetylated blown dehydrated castor oil, or more especially, hydroxyacetylated blown dehydrated triricinolein, in the presence of a minimum amount of hydroxyacetylated cogeners.

Hudromilacetylated. drasticallyoxidized dehydrated castor oil-Example 5 alcohol, denatured aliphatic alcohols, such as methyl alcohol. ethyl alcohols, hexyl alcohols, octyl alcohols, etc., may be employed as diluents. Miscellaneous solvents. such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsiiying agent of our process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone. or in admixture with other suitable well known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form,

or in an oil-soluble form, or in a form exhibiting both oil and water solubility. Sometimes they may be used in a form which exhibits relatively limited oil solubility. However, since such reagents are sometimes used in a ratio of 1 to 10,000, or 1 to 20,000, or even 1 to 30,000, such an apparent insolubility in oil and water is not significant, because said reagents undoubtedly have solubility within the concentration employed. This same fact is true in regard to the material or materials employed as the demulsifying agent of our process.

We desire to point out that the superiority ot the reagent or demulsifying agent contemplated in. our process is based upon its ability to treat certain emulsions more advantageously and at a pure or of a technical purity, and such material 'may be employed as an initial raw material.

Likewise, pure or technically pure monoricinolein or ricinoleic acid may be employed. For obvious reasons, however, nothing is ordinarily gained by using any initial raw material other than castor oil, and we have found castor oil to yield much more effective demulsiflers than the other materials referred to. Thus, our preference, by far, is

to employ castor oil as the initial raw material, and to subject it to drastic oxidation and dehydration.

In view of what has been said, it is obvious that in the hereto appended claims there cannot be any satisfactory means of characterizing the productsas such, or for use as demulsiflers, except in terminology, which is related to the method of manufacture.

The expression drastically-oxidized or drastic oxidization," as employed in the hereto appended claims, refers to gaseous oxidation by means of an oxygen-containing medium. Such expression does not contemplate wet oxidation, or oxidation by means of permanganate, or other comparable oxidizing agents.

It is furthermore understood that hydroxyacetylation can be conducted by means of the chemical equivalent of hydroxyacetic acid, as well as the acid itself, for example, the. anhydride or-acyl chloride..

Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such; or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as gasoline, kerosene, stove oil, a coal tar product, such as benzene, toluene, xylene. tar acid oil,

somewhat lower cost than is possible with other available demulsiflers, or conventional mixtures thereof. It is believed that the particular demulsiiying ent or treating agent herein described will find comparatively limited application, so far as the majority of oil field emulsions are concerned; but we have found that such a demulsifying agent has commercial value, as it will economically break or resolve oil field emulsions in a number of cases which cannot be.

treated as easily or at so low a cost with the demulsifying agents heretofore available.

In practising our process, a treating agent or demulsifier of the kind above described isbrought into contact with or-caused to'act upon the emulsion to be treated, in any of the variousways or by any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used either alone or in combination with other demulsifying procedure, such as the electrical dehydration process.

The demulsifler herein contemplated may be employed in connection with what is commonly known as down-the-hole procedure, 1. e., bringing the demulsifler in contact with the fluids of the well at the bottom of the well, or at some point prior to their emergence. This particular type of application is, decidedly feasible, when the demulsifler is used in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.

Previous reference has been made to monois perfectly clear. For instance, it has been pointed out that drastically-oxidized dehydrated castor oil may have an 'acetyl number or value cresoh'anthracene oil, etc. Alcohols, particularly of 75. This value may be considered as being alcohol, propyl alcohols, butyl 4 2,340,307 distributed over 3 acyl radicals, or to state it another way,- as being an acetyl value of 25 per acyl group. Thus, the preparation of a mono- I estolides of drastically-oxidized hydroxyacetylated product would involve 'sum-' cient reactantnso as to convert one-third of the acetyl value or number, to wit, 25. A di-hydroxyacetylated product would involve suificient reactant to convert two-thirds or the, equivalent of an acetyl value of 75. A tri-hydroizyacetylated product would involve suflicient reactant to eliminate the entire acetyl value of 75.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is: i I

1. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising a hydroxyacetylated drastically-oxidized dehydrated ricinoleic acid coin-- pound selected from the class consisting 'of drastically-oxidized dehydrated castor oil, drasticallyoxidized dehydrated triricinolein, drastically-oxidized dehydrated diricinolein, drastically-oxidized dehydrated mohoricinolein, drasticallyoxidized dehydrated ricinoleic acid, drasticallyoxidized dehydrated polyricinoleic acid, and the jecting the emulsion to the action of a demulsiv tying agent comprising mono-hydroxyacetylated drastically-oxidized dehydrated castor oil.

4. A process for breaking petroleum emulsions of the -water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising di-hydroxyacetylated drastically-oxidized dehydrated castor oil.

5. A process for breaking petroleum emulsions of the water in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprisin tri-hydroxyacetylated "drastically-oxidized dehydrated castor oil.

MELVIN DE GROO'I'E. BERNHARD KEISER. ARTHUR F. WIRTEL. 

